Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

• the present invention relates to novel ⁇ -azolyl glycols, processes for their preparation, agents for regulating plant growth which contain these compounds, and processes for regulating plant growth with these compounds.
• R 1 preferably represents a branched or unbranched alkyl radical having 1 to 4 carbon atoms, such as, for example, a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl or tert-butyl radical.
• R 2 preferably represents an alkyl radical having 1 to 6 carbon atoms, which can be unbranched, such as, for example, a methyl, ethyl, propyl, butyl or pentyl radical, or can be branched and can comprise 3 to 6 carbon atoms, such as, for example, an isopropyl -, tert .-- Butyl or a 3-methyl-butyl-l radical.
• R 2 is an unsubstituted or halogen, preferably chlorine or bromine, mono- or disubstituted phenyl or biphenyl radical.
• R 3 preferably represents hydrogen, an unbranched alkyl radical having 1 to 6 carbon atoms, such as a methyl, ethyl, propyl, butyl or pentyl radical, a branched alkyl radical having 3 to 6 carbon atoms - such as an isopropyl or iso - butyl radical, for an alkenyl or alkynyl radical having 2 to 6 carbon atoms - such as for a vinyl, ethynyl, propen-2-yl-1, propin-2-yl-1 or for a 3- Methyl - buten-2-yl-l-rest -, or for one if necessary Halogen - such as fluorine or chlorine - mono- or disubstituted benzyl radical.
• an unbranched alkyl radical having 1 to 6 carbon atoms such as a methyl, ethyl, propyl, butyl or pentyl radical
• the new ⁇ -azolyl glycols each have an asymmetry center in the acetal C atom and - if R 2 and R 3 are different - in the carbinol C atom. Depending on the nature of R 1 , additional asymmetry centers may be added.
• the compounds can be obtained in the form of uniform enantiomers or diastereomers using conventional separation methods. In practice, both the uniform enantiomers or diastereomers and the mixtures usually obtained in the synthesis can be used. The latter are preferred.
• the starting compounds II can be prepared by reacting ⁇ -halogen ethers of the formula III in which R 1 and R 2 have the meaning mentioned above and Hal is chlorine or bromine, with azoles (triazole, imidazole) or their alkali metal or alkaline earth metal salts, if appropriate in the presence of a solvent and a base at temperatures between 0 and 100 ° C.
• the d-haloethers of the formula III can be prepared by known methods (cf. DE-OS 22 01 063 and B. Mylo, Chem. Ber. 44 (1911), p. 3212, Straus and Weber Ann. 498 (1932), P. 124).
• the compounds of the formula III can also be prepared by halogenation (for example with N-bromosuccinimide) of the ⁇ -alkoxy ketones.
• alcohols of the formula V are known, such as, for example, 1,1-dimethoxy-2-methylbutin-3-ol-2 (DE-PS 17 68 877), or 1,1-dimethoxy-2-methylbutene-3 --ol-2 (DE-PS 11 15 238). However, they can also be prepared by known methods by ketones of the formula VI
• Suitable inorganic or orxanic acid halides for process c) are, for example, thionyl chloride, acetyl chloride or acetyl bromide.
• all common, easily accessible acid halides can be used.
• Suitable inorganic or organic bases which can optionally also be used as acid-binding agents in processes a or c, are, for example, alkali and alkaline earth metal hydroxides - such as sodium hydroxide, potassium hydroxide, calcium hydroxide -, alkali metal carbonates - such as potassium or sodium carbonate -, alkali metal hydrides - such as sodium hydride -, Alkali or alkaline earth alcoholates - such as sodium methylate, magnesium methylate or sodium isopropylate -, or tertiary amines - such as trimethylamine, triethylamine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, N-methylpiperidine or pyridine.
• alkali and alkaline earth metal hydroxides - such as sodium hydroxide, potassium hydroxide, calcium hydroxide -, alkali metal carbonates - such as potassium or sodium carbonate -, alkali metal
• the azoles themselves can be used as bases.
• suitable bases such as, for example, alkali metal hydride - such as sodium hydride -, lithium alkyl - such as butyllithium -, or alkali or alkaline earth metal alcoholates - such as sodium methylate - the azoles can also be used in one upstream reaction are first converted into their salts and then reacted as such.
• the preferred solvents or diluents include halogenated hydrocarbons - such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene -, aliphatic or aromatic hydrocarbons - such as cyclohexane, petroleum ether, benzene, toluene, or xylenes -, esters - such as ethyl acetate -, amides - Like dimethylformamide -, nitriles - like acetonitrile -, sulfoxides - like dimethyl sulfoxide -, ketones - like acetone or methyl ethyl ketone -, ethers - like diethyl ether, tetrahydrofuran or dioxane -, or corresponding mixtures.
• halogenated hydrocarbons - such as methylene chloride, chloroform, 1,2-dichloroethane, chloro
• Suitable reaction accelerators are preferably metal halides - such as potassium iodide -, crown ethers, quaternary ammonium compounds - such as tetrabutylammonium iodide - or acids or combinations of these reaction accelerators.
• the reactions according to the invention are generally carried out at from 0 to 150 ° C. in a period of from 1 to 60 hours, without pressure or under pressure, continuously or batchwise.
• the methods according to the invention are isolated by customary methods.
• the products obtained do not require any further purification, but they can also be purified further using known methods such as recrystallization, extraction, distillation or chromatography.
• the ⁇ -azolyl glycols of the formula I are then converted into their plant-tolerable salts or into their metal complexes by known processes.
• the following are suitable for salt formation: hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or dodecylbenzenesulfonic acid.
• the effectiveness of the salts is due to the cation, so that the choice of the anion is arbitrary.
• Metal complexes are formed by the addition of the new compounds to the cations of metal salts. Copper (II) chloride, copper (II) sulfate, copper (II) nitrate, zinc (II) chloride, iron (III) chloride, manganese (II) chloride, nickel (II) are particularly suitable for this. -bromide.
• a solution of 1- (1 ', 2', 4 '- triazole) is added to a solution of 0.2 mol of 4-chlorophenylmagnesium bromide (made from 4.9 g of magnesium and 38.3 g of 4-bromochlorobenzene) in 150 ml of ether -1'-yl) -1-methoxyacetone added dropwise in 100 ml of ether.
• the mixture is then stirred at reflux temperature for 5 hours.
• 50 g of ice and then 25% strength aqueous ammonium chloride solution are added dropwise to the cooled reaction mixture until the phases separate clearly.
• the organic phase is separated off and the aqueous phase is extracted twice with 100 ml of ether each time.
• the vegetative growth of the plants can be strongly inhibited, which manifests itself in particular in a reduction in the growth in length.
• the use of the agents can also increase or inhibit the lateral branching of the plants. There is interest in this, e.g. if in tobacco plants the formation of side shoots (stinging shoots) should be inhibited in favor of leaf growth.
• Frost resistance can also be significantly increased with the agents, for example in winter rape.
• the growth in length and the development of a lush (and therefore particularly susceptible to frost) leaf or plant mass are inhibited.
• the young rapeseed plants are retained in the vegetative development stage after sowing and before the onset of winter frosts, despite favorable growth conditions. This also eliminates the frost risk of such plants, which lead to the premature degradation of the bloom inhibition and the transition to the generative phase tend. It is also advantageous for other crops, for example winter cereals, if the stocks are well planted in autumn by treatment with compounds according to the invention, but do not go into the winter too abundantly.
• the new substances can increase yields by interfering with plant metabolism or by promoting or inhibiting vegetative and / or generative growth.
• the means can be used to shorten or lengthen the growth stages or to accelerate or delay the ripeness of the harvested parts of the plant before or after the harvest.
• Ease of harvesting is of economic interest, for example, which is made possible by the time-related falling or decreasing of the adhesive strength on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts.
• the same mechanism that is, the promotion of the formation of separating tissue between the fruit or leaf and the shoot of the plant is also essential for a well controlled defoliation of the trees.
• the effect of the new compounds is better than that of known growth regulators.
• the effect is shown both with monocots, e.g. Cereals such as wheat, barley, rye, oats and rice or corn as well as dicotyledons (e.g. sunflowers, tomatoes, soybeans, vines, cotton and especially rapeseed) and various ornamental plants such as chrysanthemums, poinsettias and hibiscus.
• the new ⁇ -azolyl glycols can be cultivated both from the seed (as a seed dressing) and via the soil, i.e. through the root, as well as by spraying over the leaf.
• active compound 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
• the agents according to the invention can be used in the form of customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
• the application forms depend entirely on the purposes; in any case, they should ensure a fine and uniform distribution of the active substance.
• the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if appropriate using emulsifiers and dispersants, it also being possible to use other organic solvents if water is used as the diluent.
• solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g.
• chlorobenzenes paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine), dimethylformamide and water; solid carriers such as natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic powdered rock (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates) and dispersants such as lignin, sulfite liquors and methyl cellulose.
• paraffins e.g. petroleum fractions
• alcohols e.g. methanol, butanol
• amines e.g. ethanolamine
• solid carriers such as natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic
• the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90.
• formulations or the ready-to-use preparations produced therefrom such as solutions; Emulsions, suspensions, powders, dusts, pastes or granules are used in a known manner, for example wise in the pre-emergence process, in the post-emergence process or as pickling agent.
• active ingredient 3 20 parts by weight of active ingredient 3 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
• a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
• active ingredient 1 40 parts by weight of active ingredient 1 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.
• active ingredient 2 20 parts are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid - urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
• the agents according to the invention can also be present in these application forms together with other active ingredients, such as e.g. Herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied.
• active ingredients such as e.g. Herbicides, insecticides, growth regulators and fungicides or also mixed with fertilizers and applied.
• growth regulators When mixed with growth regulators, the spectrum of action is enlarged in many cases.
• a number of such growth regulator blends also have synergistic effects, i.e. the effectiveness of the combination product is greater than the added effectiveness of the individual components.
• test plants spring barley, variety “Union” and summer rape, variety “Petranova" were grown in soil with sufficient nutrients in plastic containers of approx. 12.5 cm in diameter.
• the color intensity of the leaves increased in line with the reduction in length growth.
• the increased chlorophyll content also suggests an increased photosynthesis rate and thus an increased yield formation.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1980
  • 1980-12-18 DE DE19803047726 patent/DE3047726A1/de not_active Withdrawn
• 1981
  • 1981-10-23 AT AT81108806T patent/ATE7786T1/de not_active IP Right Cessation
  • 1981-10-23 EP EP81108806A patent/EP0056087B1/fr not_active Expired
  • 1981-10-23 DE DE8181108806T patent/DE3164005D1/de not_active Expired
  • 1981-11-03 GR GR66417A patent/GR75117B/el unknown
  • 1981-11-23 US US06/324,276 patent/US4436548A/en not_active Expired - Fee Related
  • 1981-12-14 JP JP56200259A patent/JPS57128674A/ja active Pending
  • 1981-12-17 IE IE2975/81A patent/IE54041B1/en unknown
  • 1981-12-17 DK DK560681A patent/DK560681A/da not_active Application Discontinuation

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